JPH07196939A - Production of synergistic pigment mixture - Google Patents

Abstract

PURPOSE: To obtain the subject mixture excellent in coloring properties and fastness properties and desirable for the coloration of plastics, printing inks, or the like, by subjecting a solution of a mixture obtained by dissolving a plurality of specified pigment compounds in an organic solvent to a treatment such as a thermal treatment.

CONSTITUTION: This mixture is obtained by dissolving at least two compounds of formula I: A(B)_x {wherein A is a chromophoric residue of such as quinacridone, anthraquinone, perylene, indigo, or azo series; B is a group of formula II [wherein X is a 1-14C alkylene, a 2-8C alkenylene; Y is a group of the formula: V-(CH₂)_q (wherein V is a 3-6C cycloalkylene; and (q) is 1-6); R₁ and R₂ are each H, a 1-6C alkyl, a 1-4C alkoxyl, a halogen, or the like; and (m), (n), and (p) are each 0 or 1], a group of formula III [wherein Z is a group of the formula: V-(CH₂)_r (wherein (r) is 0-6); and Q is H, CN, or Si(R₁)₃], a group of formula IV (wherein R₃ and R₄ are each H, a 1-18C alkyl or the like), or the like; and (x) is 1-4} in an organic solvent to obtain a mixture solution and subjecting this solution to a thermal treatment, photolytic treatment, or a chemical treatment to precipitate a mixture comprising pigments of the formula V: A(H)_x.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

The present invention relates to a process for the preparation of synergistic pigment mixtures, in particular by mixing a solution of at least two "pigments" solubilized by the introduction of carbamate groups and then incorporating them into the substrate to be colored. Before or after the treatment, the mixture is subjected to a heat treatment, a photolysis treatment or a chemical treatment to precipitate the mixture in the form of a pigment.

It has long been known from the relevant literature that certain pigment properties, including tintability and fastness, can be improved by mixing multiple pigments of the same pigment class or substantially similar pigment classes. There is. In some cases so-called solid solutions or mixed crystals are formed. For example, solid solutions of quinacridone, quinacridonequinone and / or dehydroquinacridone, which are characterized by excellent fastness and, in particular, by special coloring properties, are disclosed in US Pat. Nos. 3,160,510, 3,298,847 and 3,647,494. Calligraphy, No. 368110
No. 0 specification. US Patent 377674
No. 9 describes a mixture of an azo pigment and a soluble azo dye which has unexpectedly high tinctorial strength and transparency. Also, German Patent Publication No. 20099073 discloses a mixture of two or more perylene tetracarbodiamides having improved lightfastness and transparency compared to the individual components. German Patent Publication Nos. 3436206, 3436208,
No. 3,436,209 discloses mixed crystals of different perylene teteracarbodiimides characterized by excellent heat resistance. U.S. Pat. No. 4,720,305 describes pigment mixtures of different diketopyrrolopyrroles with improved pigment properties compared to the individual components. Also, different diketopyrrolopyrrole pigment solid solutions and diketopyrrolopyrrole pigment and quinacridone solid solutions are disclosed in U.S. Pat. No. 4,783,540 and U.S. Pat. No. 4,810,304. In both cases, the product has improved pigmentary properties compared to the individual components.

Now, according to the invention, similar pigment mixtures, solid solutions or mixed crystals, which exhibit even more surprisingly improved properties, are solubilized by introducing carbamate groups into the pigment molecule in advance of the individual components. Then dissolve the ingredients in a suitable solvent and mix in the form of a solution,
Finally, it was found that it can be obtained from this dissolved mixture by heat treatment, photolytic treatment or chemical treatment, again by precipitating the components in the form of a pigment mixture, a solid solution or a mixed crystal.

The present invention therefore relates to a process for preparing a synergistic mixture of at least two different pigments of the quinacridone, anthraquinone, perylene, indigo, quinophthalone, isoindolinone, isoindoline, dioxazine, phthalocyanine, diketopyrrolopyrrole or azo series. In the formula (I) A (B) _x (I) (wherein, x is an integer of 1 to 4, A is quinacridone, anthraquinone, perylene, indigo, quinophthalone, isoindolinone, isoindoline, dioxazine, phthalocyanine, di) A residue of a ketopyrrolopyrrole or azo series chromophore, these residues preferably being at least 1
Containing x N atoms bound to B by a directly adjacent or conjugated carbonyl group of the species, B is a group of the formula: and when x is 2, 3 or 4, then 1, 2 Or it can be 3 hydrogen atoms,

[Chemical 28]

[In the formulas II, III and IV, m, n and p are independently of each other a number of 0 or 1, X is C ₁ -C ₁₄ alkylene or C ₂ -C ₈ alkenylene and Y is -V. -(CH
₂ ) _q- group, Z is -V- (CH ₂ ) _r- group, where V is C ₃ -C
₆ cycloalkylene, q is an integer of 1 to 6, r is an integer of 0 to 6, R ₁ and R ₂ are independently hydrogen,
C ₁ -C ₆ alkyl, C ₁ -C ₄ alkoxy, halogen, C
N, NO ₂ , phenyl or phenoxy unsubstituted or C ₁ -C ₄ alkyl, phenyl or phenoxy substituted by C ₁ -C ₄ alkoxy or halogen, Q is hydrogen, CN, Si (R ₁ ) ₃ , group C (R ₅ ) (R ₆ ) (R ₇ ) (where R ₅ ,
R ₆ and R ₇ independently of each other are hydrogen or halogen, and at least one of R ₅ , R ₆ and R ₇ is halogen), a formula

[Chemical 29] (In the formula, R ₁ and R ₂ have the above meanings), a group SO
₂ R ₈ or SR ₈ (where R ₈ is C ₁ -C ₄ alkyl), the group CH (R ₉ ) ₂ (where R ₉ is unsubstituted phenyl or C ₁ -C ₄ alkyl, C _1-). C ₄ alkoxy or phenyl substituted by halogen), or a formula

[Chemical 30] Wherein R ₃ and R ₄ are independently of each other hydrogen, C ₁ -C ₁₈ alkyl or the formula

[Chemical 31] (Wherein X, Y, R ₁ , R ₂ , m and n have the above meanings) or R ₃ and R ₄ together with the nitrogen atom to which they are attached are pyrrolidinyl groups. , Forming a piperidinyl group or a morpholinyl group]} in the conventional manner in powder form and dissolving the mixture in an organic solvent, or first dissolving the individual components in an organic solvent, Then, the solutions are mixed, and then the dissolved mixture is subjected to a heat treatment, a photolysis treatment or a chemical treatment from the corresponding pigment of the formula A (H) _x (wherein A and x have the above meanings). To provide a method of precipitating.

A is a known chromophore having a basic structure A (H) _x , such as

[0007]

[Chemical 32]

[Chemical 33]

[Chemical 34]

[Chemical 35]

[Chemical 36]

[Chemical 37] And residues of all known derivatives thereof.

C ₁ -C ₁₄ alkylene for X is straight-chain or branched alkylene, examples being methylene, dimethylene, trimethylene, 1-methylmethylene,
1,1-dimethylmethylene, 1,1-dimethyldimethylene, 1,1-dimethyltrimethylene, 1-ethyldimethylene, 1-ethyl-1-methyldimethylene, tetramethylene, 1,1-dimethyltetramethylene, 2,2-dimethyltrimethylene, hexamethylene, decamethylene,
1,1-dimethyl decamethylene, 1,1-diethyl decamethylene, tetradecamethylene and the like.

The C ₂ -C ₈ alkenylene represented by X is a linear or branched alkylene, for example vinylene, arylene, metalrylene, 1-methyl-2-butenylene, 1,1-dimethyl-3-. Examples include butenylene, 2-butenylene, 2-hexenylene, 3-hexenylene and 2-octenylene. Halogen is iodine, fluorine, bromine,
Chlorine, preferably bromine, most preferably chlorine.

Examples of C ₁ -C ₆ alkyl are methyl, ethyl,
Examples of n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-amyl, tert-amyl, hexyl, and C ₁ -C ₁₈ alkyl further include heptyl, octyl, 2-methylhexyl, nonyl, Decyl, dodecyl, tetradecyl, hexadecyl or octadecyl. Examples of C ₁ -C ₄ alkoxy are methoxy,
Ethoxy, n-propoxy, isopropoxy or butoxy. Examples of C ₃ -C ₆ cycloalkylene is cyclopropylene, cyclopentylene and preferably cyclohexylene.

Compounds of formula I which are of particular interest in the practice of the present invention are compounds wherein x is 1 or 2 and B is of formula

[Chemical 38] Or a compound of formula (IV) above, and when x is 2, then one hydrogen.

In these formulas IV, V and VI, m is 0
Or 1, X is C ₁ -C ₄ alkylene or C ₂ -C ₅ alkenylene, R ₁ and R ₂ are each independently hydrogen, C ₁ -C ₄ alkyl, methoxy, chlorine or NO ₂ , Q is hydrogen ,
CN, CCl ₃ , formula

[Chemical Formula 39] The group SO ₂ CH ₃ or SCH ₃ and R ₃
And R ₄ are independently of each other hydrogen, C ₁ -C ₄ alkyl or a formula

[Chemical 40] Or R ₃ and R ₄ together form a piperidinyl group.

Preferred are compounds of formula I as defined by: where x is 2 and B is of formula

[Chemical 41] It is two of the groups.

A preferred group of compounds of formula I is summarized below. (A) Perylenecarboximide of the following formula

[Chemical 42] Wherein D is hydrogen, C ₁ -C ₆ alkyl, unsubstituted or halogen- or C ₁ -C ₄ alkyl-substituted phenyl, benzyl or phenethyl, or B,

(B) quinacridone of the following formula

[Chemical 43] In the formula, R ₁₀ and R ₁₁ are independently of each other hydrogen, halogen, C
₁ -C ₁₈ alkyl, C ₁ -C ₄ alkoxy or phenyl,

(C) Dioxazine of the following formula

[Chemical 44] Wherein R ₁₂ is hydrogen, halogen or C ₁ -C ₁₈ alkyl,

(D) Isoindoline of the following formula

[Chemical formula 45] In the formula, R ₁₃ is

[Chemical formula 46] R ₁₄ is hydrogen, C ₁ -C ₁₈ alkyl, benzyl or the formula

[Chemical 47] , R ₁₅ has the same meaning as R ₁₃ , R ₁₆ , R ₁₇ , R
₁₈ , R ₁₉ are independently of each other hydrogen, C ₁ -C ₁₈ alkyl,
C ₁ -C ₄ alkoxy, halogen or trifluoromethyl,

(E) Indigo derivative represented by the following formula

[Chemical 48] In the formula, R ₂₀ is hydrogen, CN, C ₁ -C ₄ alkyl, C ₁ -C ₄
Alkoxy or halogen,

(F) Azobenzimidazolone of the following formula

[Chemical 49] In the formula, R ₂₁ and R ₂₂ are independently of each other hydrogen, halogen, C
Is ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy,

(G) Anthraquinoid compound represented by the following formula

[Chemical 50]

(H) Phthalocyanine of the following formula

[Chemical 51] In the formula, X ₁ is H ₂ , Zn, Cu, Ni, Fe or V,
X ₂ is —CH (R ₂₄ ) — or —SO ₂ —, R ₂₃ is hydrogen,
C ₁ -C ₄ alkyl, -N (E) R ₂₄ , -NHCOR ₂₅ ,
-COR ₂₅ or

[Chemical 52] R ₂₄ is hydrogen or C ₁ -C ₄ alkyl, R ₂₅ is C ₁ -C ₄ alkyl, R ₂₆ is hydrogen, halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy, z is 0 or 1 , Y is an integer of 1 to 4,

(I) Pyrrolo [3,4-c] pyrrole of the following formula

[Chemical 53] Where G and L are independent of each other

[Chemical 54] (In the formula, R ₂₇ and R ₂₈ are independently of each other hydrogen, halogen,
C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy, C ₁ -C ₁₈ alkylmercapto, C ₁ -C ₁₈ alkylamino, -CN,-
NO _2, phenyl, trifluoromethyl, C ₅ -C _{6 cycloalkyl, -C = N- (C 1 -C} 18 alkyl),

[Chemical 55] A group of imidazolyl, pyrazolyl, triazolyl, piperazinyl, pyrrolyl, oxazolyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, morpholinyl, piperidinyl or pyrrolidinyl, and M is-
_{CH 2 -, -CH (CH 3} ) -, -C (CH 3) 2 -, -CH =
N-, -N = N -, - O-, -S-, -SO-, -SO 2 -,
Or -NR ₃₃ -, R ₂₉ and R ₃₀ are each independently of the other hydrogen, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₁₈ alkoxy or
-CN, R ₃₁ and R ₃₂ are independently of each other hydrogen, halogen or C ₁ -C ₆ alkyl, R ₃₃ is hydrogen or C ₁ -C ₆ alkyl), and in the above formulas, E is hydrogen. Or B, with the proviso that at least one E is at least one group B and B has the meanings given above, for which the preferred meanings given above also apply.

C ₁ -C represented by R ₂₇ and R _{28 in} formula XVII
Examples of ₁₈ alkyl mercapto are methyl mercapto, ethyl mercapto, propyl mercapto, butyl mercapto,
Octyl mercapto, decyl mercapto, hexadecyl mercapto or octadecyl mercapto, C _1-
Examples of C ₁₈ alkylamino are methylamino, ethylamino, propylamino, hexylamino, decylamino,
Hexadecylamino or octadecylamino.

A compound of the formula VII in which R ₁₀ and R ₁₁ independently of one another are hydrogen, chlorine or methyl and E has the meaning given above.
It is particularly preferred to use a quinacridone of I and / or a pyrrolo [3,4-c] pyrrole of the formula XVII in which G and L are the same and are of the formula:

[Chemical 56] In the formula, R ₂₇ and R ₂₈ are independently of each other hydrogen, chlorine, bromine,
C ₁ -C ₄ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylamino, CN or phenyl, M is -O-, -NR
_33- , -N = N- or -SO _2- , R ₂₉ and R ₃₀ are hydrogen, R
₃₃ is hydrogen, methyl or ethyl, E has the meaning given above.

The following formula

[Chemical 57] And / or the formula

[Chemical 58] Quinacridone and / or formula

[Chemical 59] It is especially preferred to use the pyrrolo [3,4-c] pyrrole of.

R ₂₇ and R _{28 in} formula XX independently of one another are hydrogen, methyl, tert-butyl, chlorine, bromine, CN or phenyl, and E in formulas XVIII, XIX, XX is

[Chemical 60] It is the basis of

The compound of formula I is prepared by a method similar to the known method, for example, a compound of formula A (H) _x (XXI) (wherein A and x have the above meanings) in an aprotic organic solvent. And the presence of a base as a catalyst, conveniently at a temperature of 0 to 400 ° C, preferably 10 to 20
2 to 80 hours at a temperature of 0 ° C., at desired molar ratio, dicarbonate of formula B-O-B (XXII) or trihaloacetates of formula _{(R 34) 3 C-B} (XXIII), or formula BN _3, An azide of (XXIV) or a carbonate of the formula B-OR ₃₅ (XXV), or a formula of

[Chemical formula 61] It can be produced by reacting with alkylidene-iminooxyformate.

In each of the above formulas, B has the above meaning, R ₃₄ is chlorine, fluorine or bromine, and R ₃₅ is C ₁ -C ₄
Alkyl or unsubstituted phenyl, or halogen, C ₁
-C ₄ alkyl, C ₁ -C ₄ alkoxy or phenyl which is substituted by -CN, R ₃₆ is -CN or -COO
R ₁₈ and R ₃₇ are unsubstituted phenyl, halogen, C _1-
Phenyl substituted by C ₄ -alkyl, C ₁ -C ₄ -alkoxy or —CN.

It is preferred to react the compound of formula XXI with the dicarbonate of formula XVII. A compound of formula XXI, formula X
Dicarbonates of XII, trihaloacetates of formula XXIII, azides of formula XXIV, carbonates of formula XXV, and alkylidene-iminooxyformates of formula XXVI are known compounds. If it is a new compound,
It can be produced by a method according to a standard known method. The molar ratio of the compound of formula XXI to each compound of formulas XXII to XXVI means x, ie the group B to be introduced.
Depends on the number of. However, preferably the formula XXII
To XXVI compounds are used in 2-10 fold excess.

Examples of suitable organic solvents are ethers such as tetrahydrofuran or dioxane, glycol ethers such as ethylene glycol methyl ether,
Ethylene glycol ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and also dipolar aprotic solvents such as acetonitrile, benzonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, nitrobenzene, N-methylpyrrolidone, halogenated Aliphatic or aromatic hydrocarbons such as trichloroethane, benzene or alkyl-, alkoxy- or halogen-substituted benzenes such as toluene, xylene, anisole or chlorobenzene, or aromatic N-heterocyclic compounds such as pyridine, picoline or quinoline. . Preferred solvents are tetrahydrofuran, N, N-dimethylformamide and N-methylpyrrolidone.
The solvents exemplified above can also be used in the form of a mixture. It is suitable to use 5 to 20 parts by weight of solvent for 1 part by weight of reactants.

Examples of suitable bases as catalysts are the alkali metals themselves, preferably lithium, sodium or potassium and their hydroxides or carbonates, or alkali metal amides such as lithium amide, sodium amide or potassium amide or alkali metal hydrogen. Compounds such as hydrides of lithium, sodium or potassium, as well as alkaline earth metal or alkali metal alcoholates, especially alcoholates derived from primary, secondary or tertiary aliphatic alcohols having 1 to 10 carbon atoms. , For example, lithium, sodium or potassium methylate, ethylate, n-propylate, isopropylate, n-butyrate, sec-butyrate, tert-butyrate, 2-methyl-2-butyrate, 2-methyl 2-pentylate, 3-methyl -
3-pentylates, 3-ethyl-3-pentylates, as well as organic-aliphatic, aromatic or heterocyclic nitrogen bases such as diazabicyclooctene, diazabicycloundecene and 4-dimethylaminopyridine, trialkyl Amines such as trimethylamine or triethylamine. Mixtures of these bases can also be used.

Preferred are organic nitrogen bases such as diazabicyclooctene, diazabicycloundecene, 4-dimethylaminopyridine, with 4-dimethylaminopyridine being especially preferred. The reaction is preferably 10 to 1
It is carried out at a temperature of 00 ° C., most preferably 14-40 ° C. and atmospheric pressure. To carry out the invention, the compounds of the formula I are mixed in powder form by the standard known methods in the desired proportions and the mixture is dissolved in a solvent, or
Alternatively, the compounds of formula I are first dissolved individually in a solvent and then these solutions are mixed in the desired proportions.

The following solvents can be conveniently used: Ethers such as tetrahydrofuran or dioxane, glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; polyalcohols such as polyethylene glycol, ketones such as acetone, ethyl methyl ketone, isobutyl methyl ketone or Cyclohexanone; and also dipolar aprotic solvents such as acetonitrile, benzonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, nitrobenzene, N-methylpyrrolidone, dimethylsulfoxide, halogenated aliphatic or aromatic hydrocarbons such as Trichloroethane, dichloromethane, chloroform, benzene or Alkyl - alkoxy - or halogen - substituted benzene such as toluene, xylene, anisole or chlorobenzene; aromatic N-heterocycles such as pyridine, high boiling solvents such as picoline or quinoline, further decalin, n- dodecane or kerosene,
And mixtures of these. Preferred solvents are toluene, diphenyl ether, N-methylpyrrolidone, N, N-dimethylformamide, dimethylsulfoxide, quinoline and the like.

The concentration of the compound of formula I in the solvent or solvent system depends largely on the type of solvent. In general, it is suitable to use 0.1 to 20% by weight of the compound of formula I, based on the total solution, preferably 0.2 to 5% by weight of the compound of formula I. A pigment mixture consisting of a plurality of pigments based on the compound of formula I can be precipitated from the above solution in a simple manner, ie by subjecting the dissolved mixture to any of the following treatments: (a) Heat treatment, that is, heating to 50 to 400 ° C., preferably 100 to 200 ° C., or laser irradiation; (b) Photolytic treatment, that is, exposure to a wavelength of 375 nm or less; (c) Chemical treatment, that is, Organic or inorganic acids, preferably acetic acid, toluenesulfonic acid, trifluoroacetic acid,
Treat with hydrochloric acid or sulfuric acid. After this, the precipitated product is isolated in a customary manner.

Since the compounds of formula I are usually soluble in the polymeric organic material to be colored, the polymeric organic material can also be used as a solvent. Thus, at least two compounds of formula I, each alone or as a mixture,
It can also be incorporated into the polymeric organic materials to be colored, for example plastics, paint systems or printing ink systems in a conventional manner and dissolved therein, and the pigment mixture is precipitated in situ by one of the abovementioned methods. You can The mixing ratio of the at least two compounds of the formula I which form the mixture can be chosen within a very wide range and is determined according to the desired color. If it is a binary mixture,
The weight ratio of the two components is preferably 50 to 95: 5 to 50, and more preferably 65 to 90:10 to 35.

The pigment mixture obtained by the process according to the invention, whether it is isolated from a solution and subsequently incorporated into the material to be pigmented or precipitated in situ in the substrate, is obtained by conventional methods. Compared to the mixture produced in, it has very good and improved properties. That is, hue, color purity,
It shows an improvement in both coloring properties such as color density, gloss and transparency, and fastness properties such as light fastness, weather fastness, migration fastness and heat fastness. It is also possible to obtain solid solutions by appropriate selection of the components and mixing ratios of the mixture, especially when the components and mixing ratios are selected in a known manner to result in solid solutions by conventional methods. However, according to the method of the present invention, it is possible to induce the formation of a solid solution even when the solid solution cannot be obtained by a conventional method. A solid solution can be characterized by its X-ray diffractogram which is different from the X-ray diffractogram of a physical mixture of two single components. The solid solution obtained by the present invention is specified by a line different from the combination of the X-ray diffraction patterns of the individual components. Hereinafter, the present invention will be further described with reference to examples.

Example 1 (a) 14.75 g (0.05) of 1,4-diketo-3,6-diphenylpyrrolo- [3,4-c] -pyrrole in 500 ml of tetrahydrofuran (dried over a molecular sieve).
12 mol) and 4-dimethylaminopyridine 3.23 g
27.94 g (0.128 mol) of di-tert-butyl dicarbonate was added to a mixture with (0.0264 mol).
Add in 3 portions over time. The resulting red suspension is stirred for 2 hours at room temperature with exclusion of atmospheric humidity. A dark green solution is obtained. The solvent is distilled off under reduced pressure. The yellow residue is washed with a 5% aqueous solution of sodium hydrogen carbonate, rinsed with water and dried under vacuum. Thus, 24.5 g of N, N′-di-tert-butoxycarbonyl-1,4-diketo-3,6-diphenylpyrrolo [3,4-c] pyrrole (theoretical value of 9
8%). Analysis: ¹ H-NMR (CDCl ₃ ): 7.75 (d.4H); 7.48-7.50 (m,
6H); 1.40 (s, 18H).

(B) N, N-dimethylformamide 1
1,4-diketo-3,6 in 00 ml (dried with molecular sieves)
-Bis (4-tert-butylphenyl) pyrrolo [3,3
4-c] -pyrrole 8.44 g (0.021 mol) and 4
24.29 g (0.111 mol) of di-tert-butyldicarbonate are added to a mixture with 1.49 g (0.012 mol) of dimethylaminopyridine. The resulting red suspension is stirred for 3 hours at room temperature with exclusion of atmospheric humidity. The color changes to orange. The precipitate is isolated by filtration, the residue is washed repeatedly with cold distilled water and dried in vacuo at room temperature. Thus, as a bright yellow product, N, N'-di-
tert-butoxycarbonyl-1,4-diketo-3,
11.40 g of 6-di- (4-tert-butylphenyl) -pyrrolo [3,4-c] pyrrole (90 theoretical)
%) Was obtained. Analysis: ¹ H-NMR (CDCl ₃ ): 7.69 (d.4H); 7.48 (d, 4H);
1.43 (s, 18H); 1.34 (s, 18H).

(C) N, N'-di-tert-butoxycarbonyl-1,4-diketo-3,6-diphenylpyrrolo- [3,4-c] pyrrole (a) 1.77 g and N,
N'-di-tert-butoxycarbonyl-1,4-diketo-3,6-di- (4-tert-butylphenyl)
A mixture with 0.38 g of pyrrolo [3,4-c] pyrrole (b) is dissolved in 100 ml of toluene at room temperature. The clear yellow solution is heated to 60 ° C. with stirring and 10 ml of trifluoroacetic acid are added. The mixture is heated to 90 ° C., stirred at this temperature for 20 minutes and then cooled to room temperature. The purple-red solid material is isolated by filtration, washed first with methanol, then with distilled water and placed in a vacuum tray drier at 70 ° C. This gave 0.90 g (69.2% of theory) of product. The product exhibited a purple-red color that was different from the original two components and their physical mixture. Similarly, the X-ray diffraction patterns were different, showing that a solid solution was obtained.

Example 2 (a) The procedure of Example 1 (a) was repeated. However,
This time, instead of 1,4-diketo-3,6-diphenylpyrrolo [3,4-c] -pyrrole, an equimolar amount of 1,4
-Diketo-3,6-di (p-tolyl) pyrrolo [3,4-
c] -pyrrole was used. N, N'- with a yield of 94%
Di-tert-butoxycarbonyl-1,4-diketo-
There was obtained 3,6-di- (p-tolyl) pyrrolo [3,4-c] pyrrole. Analysis : ¹ HNMR (CDCl ₃ ): 7.65 (d, 4H); 7.28 (d, 4H); 2.4
2 (s, 6H), 1.43 (s, 18H).

(B) The procedure of Example 1 (b) was repeated. However, this time 1,4-diketo-3,6-di (4-
Instead of tert-butylphenyl) pyrrolo [3,4-c] pyrrole, equimolar amounts of 1,4-diketo-3,6-di (m-tolyl) pyrrolo [3,4-c] -pyrrole were used. . N, N'-di-tert-butoxycarbonyl-1,4-diketo-3,6-di (m-tolyl) pyrrolo [3,4-c] pyrrole was obtained with a yield of 92%. Analysis : ¹ HNMR (CDCl ₃ ): 7.54-7.57 (m, 4H); 7.29-7.39
(m, 4H); 2.41 (s, 6H); 1.39 (s. 18H).

(C) 0.85 g of N, N'-di-tert-butoxycarbonyl-1,4-diketo-3,6-di (p-tolyl) pyrrolo [3,4-c] pyrrole (a) N, N'-di-tert-butoxycarbonyl-1,4
-Diketo-3,6-di (m-tolyl) -pyrrolo [3,4
-C] 500 ml of a mixture with 0.15 g of pyrrole (b)
Stirred in diphenyl ether at 40 ° C. for 1 hour,
Then diphenyl ether 20 preheated to 220 ° C
Add to ml with good stirring. 22 of this red suspension
Heat at 0 ° C for 30 minutes, then cool to 60 ° C.
The precipitated product is isolated by filtration, washed first with methanol,
Then, it is washed with distilled water and placed in a vacuum tray dryer to dry.
This gave 0.55 g (98% of theory) of product.
The X-ray diffractogram of this product was different from the original two component X-ray diffractograms, indicating that a solid solution was obtained.

Example 3 (a) Di-tert-into a mixture of 1.8 g (0.00576 mol) of quinacridone and 0.3 g (0.00246 mol) of 4-dimethylaminopyridine in 90 ml of N, N-dimethylformamide. Butyl dicarbonate 6.0 g
(0.0275 mol) is added. The resulting violet colored suspension is stirred overnight at room temperature with exclusion of atmospheric humidity.
The color changes to yellow. While stirring, add 1 part of this reaction mixture.
Pour into 00 ml of distilled water. The yellow precipitate is isolated by filtration, the residue is washed with cold distilled water and dried. Then N,
2.8 g (95% of theory) of N'-di-tert-butoxycarbonylquinacridone were obtained. Analysis: ¹ H-NMR (CDCl ₃ ): 8.74 (s.2H); 8.41 (d, 2H);
7.84 (d, 2H); 7.72 (t, 2H); 7.38 (t, 2H); 1.75 (s, 18H).

(B) 0.26 g of N, N'-di-tert-butoxycarbonyl-1,4-diketo-3,6-diphenylpyrrolo [3,4-c] pyrrole (prepared in Example 1a). And 2.50 g of N, N'-di-tert-butoxycarbonylquinacridone (a) are heated to 100C in 100 ml of toluene with good stirring. Then, with good stirring, 2.58 g of toluene-4-sulfohydrate was added and further heated to 10
Stir for 1 hour at 5 ° C. The red suspension is cooled to room temperature and filtered. The red filtration residue is washed first with methanol, then with distilled water and dried in vacuo at 60 ° C. This gave 1.68 g of product. The X-ray diffractogram of this product was consistent with that of α-quinacridone, indicating the presence of a solid solution of DPP in quinacridone.

Examples 4-11 Instead of the di-tert-butyl dicarbonate in (a) and (b) of Example 1, the formula B--O--B (B has the meaning given in the following table) is used. Then, Example 1 was repeated. A product almost identical to that of Example 1 was obtained.

[0046]

[Chemical formula 62]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Abul Iqbal, Alconseal 1732, Switzerland 202, Switzerland (72) Inventor Joan S. Tsambounis 3280, Mürten, Switzerland, Engelhard Strasse 41 (72) Inventor Bernhard Medinger, Switzerland 1735, Giffers, Glottenweck (no street number)

Claims (6)

[Claims] 1. A process for preparing a synergistic mixture of at least two different pigments of the quinacridone, anthraquinone, perylene, indigo, quinophthalone, isoindolinone, isoindoline, dioxazine, phthalocyanine, diketopyrrolopyrrole or azo series, wherein (I) A (B) _X (I) {wherein x is an integer of 1 to 4, A is quinacridone, anthraquinone, perylene, indigo, quinophthalone, isoindolinone, isoindoline, dioxazine, phthalocyanine, diketopyrrolopyrrole. Or residues of an azo series chromophore, these residues preferably being at least 1
Containing x N atoms bound to B by two immediately adjacent or conjugated carbonyl groups, B is a group of the formula: and when x is 2, 3 or 4, then 1, 2 or It can also be 3 hydrogen atoms, [In formulas II, III and IV, m, n and p are each independently a number of 0 or 1, X is C ₁ -C ₁₄ alkylene or C ₂ -C ₈ alkenylene, and Y is -V- (CH ₂ ) _q- group, Z
A group, V is C ₃ -C ₆ cycloalkylene, q is an integer of 1 to 6, r is 0 to 6 integer, - the -V- (CH _{2) r}
R ₁ and R ₂ are independently of each other hydrogen, C ₁ -C ₆ alkyl, C _1-
C ₄ alkoxy, halogen, CN, NO ₂ , unsubstituted phenyl or phenoxy, or C ₁ -C ₄ alkyl, C _1-
Phenyl or phenoxy substituted by C ₄ alkoxy or halogen, Q is hydrogen, CN, Si (R ₁ ) ₃ , a group C (R ₅ ) (R ₆ ) (R ₇ ) (wherein R ₅ , R ₆ , R ₇ is independently hydrogen or halogen, and at least one of R ₅ , R ₆ , and R ₇ is halogen), and has the formula: (In the formula, R ₁ and R ₂ have the above meanings), a group SO
₂ R ₈ or SR ₈ (where R ₈ is C ₁ -C ₄ alkyl), the group CH (R ₉ ) ₂ (where R ₉ is unsubstituted phenyl or C ₁ -C ₄ alkyl, C _1-). C ₄ alkoxy or phenyl substituted by halogen), or a compound of formula Wherein R ₃ and R ₄ are independently of each other hydrogen, C ₁ -C ₁₈ alkyl or the formula (Wherein X, Y, R ₁ , R ₂ , m and n have the above meanings) or R ₃ and R ₄ together with the nitrogen atom to which they are attached are pyrrolidinyl groups. , Forming a piperidinyl group or a morpholinyl group]} in the conventional manner in powder form and dissolving the mixture in an organic solvent, or first dissolving the individual components in an organic solvent, Then, the solutions are mixed, and then the dissolved mixture is subjected to a heat treatment, a photolysis treatment or a chemical treatment from the corresponding pigment of the formula A (H) _x (wherein A and x have the above meanings). A method characterized by precipitating. 2. Formula I, wherein x is 1 or 2 and B is of the formula: Or a group of the above formula (IV), and when x is 2, it may be one more hydrogen, in these formulas IV, V and VI, m is 0 or 1, X is C ₁ -C ₄ Alkylene or C ₂ -C ₅ alkenylene, R ₁ and R ₂ independently of one another are hydrogen, C ₁ -C ₄ alkyl, methoxy, chlorine or NO.
₂ and Q is hydrogen, CN, CCl ₃ , the formula: A group of SO ₂ CH ₃ or SCH ₃ , and R ₃
R ₄ independently of one another is hydrogen, C ₁ -C ₄ alkyl or of the formula 2. The process according to claim 1, characterized in that a compound of the formula (1), or R ₃ and R ₄ together form a piperidinyl group). 3. Formula I, wherein x is 2 and B is of the formula: 2. A method according to claim 1, characterized in that two different compounds (which are two of the groups 4. The method according to claim 1, wherein two different compounds selected from the following group are used: (a) Formula A perylenecarboximide, wherein D is hydrogen, C ₁ -C ₆ alkyl, unsubstituted or halogen- or C ₁ -C ₄ alkyl-substituted phenyl, benzyl or phenethyl, or B), ( b) Formula (In the formula, R ₁₀ and R ₁₁ are independently of each other hydrogen, halogen,
C ₁ -C ₁₈ alkyl, C ₁ -C ₄ alkoxy or phenyl), quinacridone, (c) formula A dioxazine of the formula: wherein R ₁₂ is hydrogen, halogen or C ₁ -C ₁₈ alkyl; [Wherein, R ₁₃ is represented by the formula: R ₁₄ is hydrogen, C ₁ -C ₁₈ alkyl, benzyl or a group of the formula The group R ₁₅ has the same meaning as R ₁₃ , where R _15
16 , R ₁₇ , R ₁₈ and R ₁₉ are independently hydrogen, C ₁ -C
₁₈ alkyl, C ₁ -C ₄ alkoxy, halogen or trifluoromethyl)] isoindoline, (e) a compound of formula (In the formula, R ₂₀ is hydrogen, CN, C ₁ -C ₄ alkyl, C ₁ -C
₄ alkoxy or halogen), an indigo derivative of formula (f): (In the formula, R ₂₁ and R ₂₂ are independently of each other hydrogen, halogen,
C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy), azobenzimidazolone, (g) having the formula: Anthraquinoid compound of formula (h): (In the formula, X ₁ is H ₂ , Zn, Cu, Ni, Fe or V, X ₂ is —CH (R ₂₄ ) — or —SO ₂ —, R ₂₃ is hydrogen, C ₁ -C ₄ alkyl, —N (E) R ₂₄ ,-NHCOR
₂₅ , -COR ₂₅ or R ₂₄ is hydrogen or C ₁ -C ₄ alkyl, R ₂₅ is C ₁ -C ₄ alkyl, R ₂₆ is hydrogen, halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy, z is 0 or 1 , Y is an integer of 1 to 4), and (i) a compound represented by the formula: [Wherein G and L are independently of each other (In the formula, R ₂₇ and R ₂₈ are independently of each other hydrogen, halogen,
C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy, C ₁ -C ₁₈ alkylmercapto, C ₁ -C ₁₈ alkylamino, -CN,-
NO ₂ , phenyl, trifluoromethyl, C ₅ -C ₆ cycloalkyl, -C = N- (C ₁ -C ₁₈ alkyl), formula: A group of imidazolyl, pyrazolyl, triazolyl, piperazinyl, pyrrolyl, oxazolyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, morpholinyl, piperidinyl or pyrrolidinyl, M is -CH
_{2 -, -CH (CH 3)} -, -C (CH 3) 2 -, -CH = N-
, -N = N -, - O- , -S-, -SO-, -SO 2 -, or -NR ₃₃ -, R ₂₉ and R ₃₀ are each independently of the other hydrogen, halogen, C ₁ -C ₆ alkyl , C ₁ -C ₁₈ alkoxy or-
CN, R ₃₁ and R ₃₂ independently of one another are hydrogen, halogen or C ₁ -C ₆ alkyl, R ₃₃ is hydrogen or C ₁ -C ₆ alkyl)]] pyrrolo [3,4-c ] Pyrrole, in each of the above formulas E is hydrogen or B, provided that at least one E is at least one group B and B has the meaning given above. 5. A formula V in which R ₁₀ and R ₁₁ independently of one another are hydrogen, chlorine or methyl and E has the abovementioned meaning.
A quinacridone of III and / or G and L are of the same type and have the formula (In the formula, R ₂₇ and R ₂₈ are independently of each other hydrogen, chlorine, bromine, C ₁ -C ₄ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆
Alkylamino, CN or phenyl, M is -O-,-
NR ₃₃ , -N = N- or -SO _2- , R ₂₉ and R ₃₀ are hydrogen, R ₃₃ is hydrogen, methyl or ethyl, and E has the meaning given above), and the pyrrolo [3, 4-c]
The method according to claim 4, wherein pyrrole is used. 6. The formula: And / or the formula A quinacridone and / or a formula Use of pyrrolo [3,4-c] pyrrole (wherein R ₂₇ and R _{28 in} formula XX independently of one another are hydrogen, methyl, tert-butyl, chlorine, bromine, CN or phenyl). Wherein E in formulas XVIII, XIX, XX is of the formula It is the basis of